Sulfur dyes and process of making same.



HEINRICH HEIMANN AND PAUL VIRGK,v 0F

ESSA G RMANY. A I B T0 ACTIEN GESELLSCHAF'I' FIIR ANILIN FABRIKATION, OF BERLIN, GERMANY.

SULFUR DYES AND PROCESS OF MAKING SAME.

No Drawing.

Specification of Letters Patent. Application filed February 26, 1913.

Patented June 2, 1914. Serial No. 750,887.

.To all whom/ it may concern:

Be it known that We, HEINRICH HEIMANN and PAUL VmoK, citizens of the German Empire, residing at Dessau, Germany, our p'ostofiice addresses being, respectively, Friedrich- Schneider strasse 63, Dessau, Germany, and Elisabethstrasse 40, Dessau, German have invented certain new and useful mprovements in Sulfur Dyes and Processes of Making Same, of which the following is a specification.

We have found. that new valuable sulfur dyes are obtained by acting with sulfur or a polysulfid or another suitable sulfurizing agent upon mixtures of a derivative of parahydroxydiphenylamin possessing the general formula:

the invention in its Widest scope as to manufacture and new products, more especlally those dyes and the manufacture thereof' which are obtained with the intervention means an alkyl group of an amin of the naphthalene series. Our new dyes thus obtained produce on cotton from a dye-bath containing an alkali-sulfid deep and full tints varying, generally speaking, from brown to black, which tints possess a very good fastness to washing and which tints are very-remarkably fast to chlorin, the fastness in this latter direction (greatly surpassing that of the known sulfur yes.

In order to manufacture our new dyes we heat the parent material with sulfur alone to high temperatures; but We may as well not with a suitable mixture of an alkali sulfid and sulfur, such as for instance with a polysulfid of a'high percentage of sulfur, or with a mixture of a caustic alkali and splfur upon a mixture of the above defined c ass.

The following examples may serve to illustrate our invention, the parts being by weight.

1. A mixture of 40 arts of para-methylpara-hydroxydipheny amin, 28 parts of alpha-naphthylamin and parts of sulfur is heated during about 4 hours to about 200 6., an oil-bath preferably being used. Then the temperature is gradually raised within about 8 hours to about 250 C. The melt thus obtained is soluble in an alkali-sulfid solution, from which solution the new dye may be separated in the usual manner, for instance by introducing a current of air. The new dye thus obtained forms in the dry shape when pulverized a black powder which is practically insoluble or very diiiicultly soluble in the usual solvents, such as glacial acetic acid, benzene, nitrobenzene, anilin, pyridin and chlorobenzenes. It dissolves in concentrated sulfuric acid to a violet-black solution and in 25% oleum (fuming sulfuric acid) to a black solution, which solutions on the addition of aluminium powder are grad- .ually decolorized. This new dye produces on cotton from a dye-bath containing an alltali-sultid deep and full violet-brown tints which resist very well the usual chlorin test with bleaching powder.

2. 20 parts of para-methyl-para-hydroxy diphenvlamin. 15 parts of alpha-naphthylamin, 2.:- parts of sulfur and 10 parts of soda-lye l-3 B6.) are. thoroughly mixed together; this mixture is at first heated during about T12 hours to PLO-180 (l, whereupon the temperature is raised and the mass is heated at about 200 C. during 7-12 hours. In order to separate the new dye one may proceed in the usual manner by dissolving the melt in an alkalisullid and introducing a current of air. But the new dye may also be separated by the addition of common salt to the afcre-said solution. The new dye thus obtained produces on cotton from a dye-hath containing an alkali-sulfid deep v YlOlCi-lHT/Yll hades of a ver remarkable fastness to ehlorin.

itccording to the foregoing! indications a new dve ma also be prepared from a mixture of paraanethvhp: rahydroxydiphenylamin with beta-naphthvlamin. The new dye which can thus he obtained resembles ver v much the product as manufactured aC- cording' to Example 2.

It obvious to those skilled in the art that our pre ent invention is not limited to the foregoing; examples or to the details given therein. Fir tlv we may state that the special condit ons of the reaction, such as for instance the duration ofthe heating or the temperature to be taken as well as the proportions of the respective ingredients, may be varied within wide limits and the results obtained accordingly may vary to some extent. Furthermore. instead of the two naphtlrvlamins used in the foregoing examples. for in tance halogenated or nitrated derivatives of naphth rlamin or naphthylenediamins or derivatives thereof may be employed. On the other hand other alliylated para-ox}'diphenylamins. such as for instance meta"unethvhparaexydiphenylamin or para, ortho'-dinlethvl-para-oxydiphenylamin may be e iplovetl. The. new dyes obtained in this way p ssess similar qualities to the dyes the manufacture of which is given above. \l'e ma also state that instead of the aromatic amins' the correspond ing" nitro compounds can be employed; it is obvious that in using such nitro compounds the special. C nditions of reaction may be altered in order to obtain the best results.

Having: now de cribed our invention and the manner in which it may be performed what we claim is.-

1. The hereiil iefore-descrilled manufacture of new sulfur dye which comprises heating with i sulfurizcing agent a mixture of an aromatic amin with certain derivatives ofpara-bydroxydiphenylamin possessing the general formula:

in which formula R means an alkyl group and w a number less than 6.

2. The hereinbefore described manufacture of new sulfur dyes which comprises heating with a sulfurizing agent a mixture of an amin of the naphthalene series with certain derivatives of para-hydroxvdiphenylamin possessing the general formula:

l l v in which formula R means an alliyl group and a a number less than 6.

4. The hereinbeforedescribed manufacture of new sulfur dves which comprises heating with a sulfurizing agent a mixture of a naphthylamin with certain derivatives the general formula:

in which formula R means an alkyl group.

5, The hereinbeforedescribed manufacture of new sulfur dyes which comprises heating with a sulfurizing agent a mixture of alpha-naphthylamin with para-methylpara-hydroxydiphcnylamin.

6. The hereinbefore-described. manufacture of new sulfur dyes which comprises heating with sulfur a mixture of alphanaphthylamin with para-methyl-para-hydroxydiphenylamin.

7. The hereinbeforedescribed manufacturn of new sulfur dyes which comprises lmating with sulfur and soda-lyea mixture of alpha-naphthyla1nin with para-methylpara-hydroxydiphenylamin.

8. As new articles of manufacture new sulfur dyes derived from certain derivatives of para-hydroxydiphenylamin possessing the general formula in which formula R means an alkyl group and an a number less than 6, in conjunction with aromatic amius, these new dyes in the dry shape when pulverized being, generally speaking, black powders, which are substantially insoluble in the usual solvents and solable in concentrated sulfuric acid and in 257, oleum (fuming sulfuric acid), generally speaking. to black solutions, and these new dyes being soluble in an alkali-sulfid and soluble in an alkaline hydrosulfite solution, from which solution cotton is dyed, generally speaking, brown to black tints, and these new dyes producing on cotton from a dye-bath containing an alkali, sulfid, generally speaking, brown to black tints,

which tints are fast to Washing and re markably fast to chlorin.

9. As new articles of manufacture new sulfur dyes derived from certain derivatives of para-hydroxydiphenylamin possessing the general formula:

a H in which formula R means an alkyl group, in conjunction with aromatic amine, these new dyes in the dry shape when pulverized being, generally speaking, black powders, which are substantially insoluble in the usual solvents, and soluble in concentrated sulfuric acid and in 25% oleum (fuming sulfuric acid), generally speaking, to black solutions, and these new dyes being soluble in an alkali sulfid, and soluble in an alkaline hydrosulfite solution, from which solution cotton is dyed, generally speaking, brown to black tints, and these new dyes producing on cotton from a dye-bath containing an alkalisulfid, generally speaking, brown to black tints, which tints are fast to washing and are remarkably fast to chlorin.

10. As a new article of manufacture a new sulfur dye derived from para-'-methy.l-parahydroxydiphenylamin in conjunction with alpha-naphthylamin, which new dye in the dry shape when pulverized forms a black powder substantially insoluble in glacial acetic acid, alcohol, benzene, nitrobenzene, anilin, pyridin and chlorobenzenes, and which new dye dissolves in concentrated sulfuric acid to a violet-black solution and in 25% oleum to a black solution, which solutions by addition of aluminium powder are gradually decolorized, this new dye dising witnesses.

HEINRICH HEIMANN. PAUL VIRCK. lVitnesses:

RUDOLPH FRICKE, Dome KRAHL. 

